CN109821486B - Method and equipment for processing phase-change material - Google Patents
Method and equipment for processing phase-change material Download PDFInfo
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- CN109821486B CN109821486B CN201910089008.2A CN201910089008A CN109821486B CN 109821486 B CN109821486 B CN 109821486B CN 201910089008 A CN201910089008 A CN 201910089008A CN 109821486 B CN109821486 B CN 109821486B
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Abstract
A processing method and equipment of a phase-change material belong to the field of functional materials. The processing equipment of the phase change material comprises: a working chamber, an air pump, a crushing mechanism and a restraint device. The working chamber is provided with a first operation area, a second operation area and a third operation area which are sequentially arranged and are respectively provided with operation gloves. The second operational zone can optionally be in communication with or isolated from either or both of the first operational zone and the third operational zone. The first operation area is provided with a first material port capable of being closed and opened, and the third operation area is provided with a third opening capable of being closed and opened. The air pump is connected with the first operation area, the second operation area and the third operation area and can respectively and independently pump any one or more of the first operation area, the second operation area and the third operation area. The shredder mechanism is located in the second operating zone. The restraint is provided with a cavity. The processing equipment can realize that the oxygen content of the phase-change material exceeds the standard in the environment that the phase-change material is used for treating anhydrous water and oxygen.
Description
Technical Field
The application relates to the field of functional materials, in particular to a method and equipment for processing a phase change material.
Background
With the research and development of a new generation of phase change non-volatile memory chips (RePCM, or PCM), various new materials have gained high attention and wide application in this field. Materials exhibiting nonlinear current-voltage (I-V Curve) properties are well suited and have been used in Non-Volatile Memory (Non-Volatile Memory) chips based on phase change materials.
The microstructure of the film of the material can be changed rapidly (switched from an amorphous state to a crystalline state) within a time of 10 ns-100 ns under the driving of a pulse voltage, and can represent a digital 0 or 1 according to the microstructure, so that the aim of information storage reading/writing is fulfilled. The switching rate between the amorphous and crystalline states is a very critical specification for phase change memory chips (RePCM). Since the switching rate determines the speed and speed of the "read" and "write" of the memory chip. The main determinant of physical mechanism is the time required from amorphous to crystalline, the so-called phase transition.
The time required for the phase change of the material is closely related to the composition, microstructure, thickness of the formed film, heat treatment of the material, heat conduction environment around the memory cell of the chip, and the like of the compounds.
Therefore, a new method for improving the phase change speed of the phase change nonvolatile memory chip manufacturing material is needed.
The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Based on the shortcomings of the prior art, the present application provides a method and apparatus for processing phase change materials to partially or fully improve or even solve the above problems.
The application is realized as follows:
in a first aspect, examples of the present application provide a phase change material processing apparatus.
The phase change material mentioned in the examples is suitable for fabricating non-volatile memory chips.
The processing equipment of the phase change material comprises:
the working chamber is provided with a first operation area, a second operation area and a third operation area which are sequentially arranged and are respectively provided with operation gloves, the second operation area can be optionally communicated or isolated with any one or both of the first operation area and the third operation area, the first operation area is provided with a first material port which can be closed and opened, and the third operation area is provided with a third opening which can be closed and opened;
the air pump is connected with the first operation area, the second operation area and the third operation area and can respectively and independently pump air to any one or more of the first operation area, the second operation area and the third operation area;
the crushing mechanism is positioned in the second operation area;
and the restraint device positioned in the second operation area is provided with a cavity.
The processing equipment proposed in the example can provide a plurality of spaces arranged as required, and adjacent spaces can be communicated or isolated as required, and further, each space can be independently purged of water and oxygen, respectively. In this manner, the processing tool allows for the input of feedstock in a desired environment while allowing the feedstock to be processed in a water and oxygen free environment, further outputting the product in a desired environment. The raw materials for manufacturing the phase-change material can be processed in an isolated environment, so that the raw materials can be prevented from directly contacting/adsorbing oxygen and water, and the oxygen content of the phase-change material serving as a final product can be controlled.
With reference to the first aspect, in some optional examples of the first possible implementation manner of the first aspect of the present application, the processing apparatus of the phase change material includes:
and the gas supply mechanism is connected with the first operation area, the second operation area and the third operation area and can respectively and independently inject gas into any one or more of the first operation area, the second operation area and the third operation area.
Gas supply means are provided for injecting gas into the various operating zones of the working chamber. And the gas injection operation can drive out various gases in the operation area. The insufflation operation may also inject a desired gas into the operating space so that the operating space is filled with the desired gas.
With reference to the first aspect, in some optional examples of the second possible implementation manner of the first aspect of the present application, the processing apparatus of the phase change material includes:
and an enclosure mechanism configured to hermetically enclose the restraint such that the restraint is enclosed in an oxygen and water free environment.
After the raw materials for manufacturing the phase-change materials are processed, the processed raw materials can be isolated from external water and oxygen all the time through the packaging mechanism after being constrained by the cavity of the constraining device, so that the processed raw materials can be isolated from the water and the oxygen all the time before being further processed, the raw materials are prevented from being polluted, and the purity of the raw materials is kept.
In combination with the first aspect, in some alternative examples of the third possible implementation of the first aspect of the present application, one or more of the first operating zone, the second operating zone, and the third operating zone is provided with an environmental condition detector, the environmental condition detector including one or more of a temperature sensor, a humidity sensor, and an oxygen sensor.
The provision of the ambient condition detector enables the various conditions within the processing equipment that affect the processing operation to be fully and accurately known so that the operator can make adjustments to the specific situation.
With reference to the first aspect, in some alternative examples of the fourth possible implementation manner of the first aspect of the present application, the processing apparatus of the phase change material includes a housing, and the working chamber, the air pump, the pulverizing mechanism, and the restrainer are disposed in the housing.
The housing may provide a relatively independent space for the working chamber, the air pump, the shredder mechanism and the restraint.
In a second aspect, examples of the present application provide a method of processing a phase change material.
The processing method comprises the following steps:
providing a closed space, wherein oxygen and water are removed from the closed space;
crushing raw materials into powder in the closed space, wherein the raw materials are from compounds formed by elements forming the phase-change material;
and (3) constraining the powder in a preset cavity in the closed space and optionally carrying out subsequent vacuum hot pressing treatment.
Treatment of the feedstock from which the phase change material is made in a space excluding oxygen and water avoids contact with and adsorption of water and oxygen, thereby ensuring that the final product obtained from the feedstock is at a relatively low oxygen content.
In some alternative examples of the first possible embodiment of the second aspect of the present application in combination with the second aspect, the enclosed space is in a vacuum state or filled with an inert gas or filled with a reducing gas;
optionally, when the enclosed space is filled with an inert gas or a reducing gas, the enclosed space is at a positive pressure relative to the atmospheric pressure;
optionally, the inert gas is argon;
alternatively, the reducing gas comprises a mixed gas of nitrogen and hydrogen; more preferably, the volume content of the hydrogen in the mixed gas is 2-5%. The use of this ratio makes it possible to maintain the incombustibility of this mixed gas.
According to the processing mode of the raw material of the phase-change material, the phase-change material can ensure that the phase-change material cannot adsorb the substances in the environment without water or oxygen. In this way, the raw material can be ensured from being contaminated.
In combination with the second aspect, in some alternative examples of the second possible implementation of the second aspect of the present application, the compound formed of the elements constituting the phase change material is obtained by vacuum melting, and the compound includes a chalcogen compound.
Optionally, the chalcogen compound comprises Ge2Sb2Te5、Cx[Ge2Sb2Te5]y、Sc0.2Sb2Te3、Ta0.3Sb2Te3、InGe2Sb2Te5、CuGe2Sb2Te5GeSbTeIn and AgInSbTe, wherein the value range of x is 1-18 at%, and x + y is 100 at%.
The chalcogen element has a plurality of excellent performances and is suitable for being used as a raw material of a phase-change material to manufacture a phase-change nonvolatile memory chip.
In combination with the first aspect or the first or second possible implementation manner of the first aspect, in some optional examples of the third possible implementation manner of the first aspect of the present application, before constraining the powder to the preset cavity in the closed space, the processing method includes: the powder was sieved.
The sieving operation enables the particle size of the powder to be more uniform, facilitating contact between particles, and thus facilitating shaping and reaction by means of pressurization, heating, and the like.
In some alternative examples of the fourth possible embodiment of the second aspect of the present application, in combination with the second aspect, the powder has a density of less than or equal to 66% in the filling of the constrainer.
The filling density of the powder is properly controlled, and the powder can be filled under the condition of relatively easy implementation, and meanwhile, the powder is not too loose to be beneficial to stacking forming and reaction.
Has the advantages that:
the processing equipment that this application embodiment provided sets up a plurality of spaces that can communicate each other and keep apart, and this each space can also carry out gas and get rid of the processing to there is adverse effect to phase change material's preparation raw materials in can being with the space mentioned if oxygen and water get rid of, and then realized processing the raw materials in the environment to raw materials safety, guarantee that the raw materials can also restrain the promotion of oxygen content when being handled as the expectation state.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments or the prior art of the present application, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a schematic structural diagram of a phase change material processing apparatus according to an embodiment of the present disclosure.
Icon: 100-a working chamber; 101-a first operating zone; 102-a second operating zone; 103-a third operating zone; 200-an air pump; 201-gas supply means; 300-handling gloves; 400-a valve; 401-a crushing mechanism; 402-a screening device; 403-a constrainer; 404-packaging mechanism.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of a method and an apparatus for processing a phase change material according to an embodiment of the present application:
phase change materials have outstanding advantages as materials for fabricating Non-Volatile Memory (Non-Volatile Memory) chips. One important property of phase change materials that affects non-volatile memory is the phase transition speed of the phase change material, i.e., the speed of transition between the amorphous and crystalline states.
To the best of the applicant's knowledge, the factors influencing the phase transition speed of the phase change material mainly include the composition, microstructure, thickness of the formed film, heat treatment of the material, and the heat conduction environment around the phase change material. Although the above factors have been confirmed to play a large role in the phase transition speed of the phase change material, such factors are not easily implemented to improve the performance of the phase change material.
For example, the composition of the phase-change material is not easy to select, and the suitable material composition is many, and the selection difficulty is large. The microstructure of the phase-change material or the finished product (such as a film) thereof has poor controllability and consistency, and a high-repeatability product is difficult to obtain.
In practical studies, applicants have found and appreciated that the oxygen content ([ O ]) of phase change materials can also play a significant role in the phase transition speed. In some examples, the results indicate that: the phase change material has low oxygen content and relatively fast phase change speed, so that the memory chip made of the phase change material has relatively fast memory speed.
In view of the above, the applicant proposes a scheme for controlling the oxygen content of the phase change material. In an example, in the process of producing the phase-change material, the oxygen content of the phase-change material is controlled, so that the phase-change material with low oxygen content is produced in a large scale.
In the related art research, the new generation of phase change memory chips can use chalcogenide compounds as raw materials to fabricate phase change materials.
For example, the related chalcogen compound is first made into a sputtering target of the phase-change material by a powder metallurgy manufacturing method, and then the phase-change material on the target is converted into a thin film for manufacturing a chip by plasma sputtering. The cell of the RePCM is manufactured by the processes of sputtering coating, photoetching, etching and the like.
In light of the foregoing, the phase change material has a low oxygen content, and can affect the oxygen content of the phase change film on the RePCM to a considerable extent, thereby directly affecting the data storage speed of the RePCM, and the performance of the memory chip.
Therefore, how to control the oxygen content of the phase-change material is a problem to be solved.
In practice, the applicant has implemented a method for obtaining a target material for making a memory chip based on a phase-change material of a chalcogen element (e.g. Se, Te; which may also generally contain other elements, such as Sb, In, Ge, Cu, Ag, Sc, Ta, etc.). The manufacturing method of the target can be described as follows:
(1) chalcogen compounds (e.g. Ge)2Sb2Te5、CGe2Sb2Te5GeSbTeIn, AgInSbTe, etc.) in a vacuum to form a block-shaped material.
For example, the chalcogen compound is Ge2Sb2Te5. Will form Ge2Sb2Te5The simple substances of the elements are put into a high-purity quartz tube according to the metering ratio. And directly vacuumizing the quartz tube, and then sealing the exhaust tube to ensure that the quartz tube is completely in a closed state.
The vacuumizing can avoid the oxidation of each element in the heating and smelting process. The vacuum pumping can also form higher vapor pressure in vacuum melting, so that the proportion of each atom in the sealed quartz tube can be maintained.
And putting the sealed and vacuumized quartz tube into a heating furnace for heating, and heating from room temperature to the expected temperature according to the preset heating speed. The quartz tube may also be mechanically shaken during the process at a desired temperature for a period of time to ensure that the elements of the quartz tube react sufficiently under high temperature and vibration.
After the full reaction is carried out under the conditions of vacuum and high temperature, all the substances are naturally cooled in a quartz tube under the vacuum condition, and disordered and freely moving atoms are crystallized to form ordered arrangement under the action of thermodynamics and kinetics. I.e., the compounds are formed in a stoichiometric ratio of the compounds.
(2) Pulverizing into powder on a ball mill, and sieving according to the required size to prepare the powder.
The chalcogen compound obtained in the above step (1) is pulverized by a ball mill to make it easier to mix and also to facilitate subsequent sintering, thereby also promoting further reaction.
(3) The powder was charged into a graphite mold.
Graphite has the desired reaction inertness, not to react easily with the aforementioned chalcogen compounds, while also being able to constrain the powder so that it can be hot pressed.
(4) And putting the die into a vacuum hot-pressing furnace cavity, vacuumizing the cavity, and sintering and compactly molding the powder in the die at a proper temperature and under a proper high pressure.
After the powder is restrained in the die, the particles in the powder are mutually contacted and reacted through vacuum hot pressing treatment.
(5) The formed embryo is machined into a certain geometric shape and is bound to a back plate of a sputtering machine.
Memory chips are typically fabricated as chip structures (typically available by sputtering) and then processed through appropriate semiconductor processing. For this purpose, the shaped material obtained by vacuum hot pressing in step (4) is processed into an appropriate shape so as to be subjected to, for example, sputtering treatment.
The applicant considers and confirms that the step (2) and the step (3) in the above steps are main links for increasing the oxygen content in the phase-change material target material.
In the step (2), the surface area of the phase-change material making raw material is exponentially increased along with the milling process. If the powder is made without the protective gas, the oxygen and water vapor in the atmosphere will be adsorbed on the newly increased surface area immediately, so the oxygen content of the material itself will be increased rapidly along with the increase of the surface area. Also, if the temperature of the powder increases during milling, there is sufficient opportunity for elements in the phase change material, such as Ge, Sb, Te, etc., to form surface oxides.
In the step (3), during the process of transferring the powder to the graphite mold, the powder will inevitably adsorb oxygen and water vapor in the air, but the adsorption degree is less than that in the step (2), because the surface of the phase-change material is adsorbed [ O ] and the water vapor is close to saturation in the step (2).
Step (4) also allows, to some extent, the material to adsorb more or less [ O ] and moisture in the atmosphere during the process of loading the mold into the vacuum hot press cavity, depending on the time used for the process and the humidity and temperature of the immediate ambient environment, etc.
In summary, step (2) is the main process flow for generating high oxygen content. The oxygen content [ O ] of the phase change memory chip produced by the above process flow is usually higher than 1000 ppm. This oxygen content slows the speed of writing/reading the produced RePCM chip, especially the speed of "writing" data to the memory cells of the chip, and thus the overall specifications of the chip are degraded.
Based on the above recognition, the applicant proposes a new phase change material processing device.
Referring to fig. 1, the apparatus for processing a phase change material includes a working chamber 100, an air pump 200, a pulverizing mechanism 401, and a restrainer 403. The shredder mechanism 401 and the restraint 403 are located in the appropriate position in the working chamber 100, the air pump 200 is incorporated into the working chamber 100 with its air inlet obviously located in the working chamber 100 and its air outlet located outside the working chamber 100. The working chamber 100 provides a space for storing and placing various equipments and materials. The crushing structure and restraint 403 is a device for processing phase change material feedstock. The air pump 200 is used to create a water-free and oxygen-free environment at different desired locations within the working chamber 100 to avoid adsorption of oxygen and water by the raw materials. The devices installed in the working chamber can be optionally fixed by bolts, rivets and other connectors so as to be replaced and maintained when needed and necessary.
The working chamber 100 is a substantially shell-like structure having a cavity of a predetermined volume defined by enclosing walls. Obviously, the walls are made of a material with suitable strength and rigidity to support their stable configuration (especially in conditions where the cavity has a considerable degree of vacuum). For example, the walls of the chamber 100 are made of stainless steel, which is plated, such as chrome plated, on the surface of the stainless steel. The wall thickness of the shell wall may also be suitably selected, e.g. 10mm, 20mm, 30mm, etc.
The studio 100 is divided into a plurality of different areas as necessary, and each area is designed according to the intended function. In the exemplary embodiment, the working chamber 100 has a first operating zone 101 (charging transition chamber), a second operating zone 102 (working zone) and a third operating zone 103 (discharging transition chamber). The three regions are arranged in sequence, i.e. the second operating region 102 is located between the first operating region 101 and the second operating region 102. The volumes of the three operating zones can be selectively arranged as desired to meet the actual processing requirements. It will be appreciated that the workroom is mostly made of transparent material (of suitable strength, such as plexiglas, etc.) in order to provide an adequate field of view for ease of handling and observation.
In addition, since the working chamber 100 needs to provide a space isolated (physically) from the external environment as needed in actual operation, the three operation areas are provided with the operation gloves 300 based on the operation needs. The operating gloves 300 are located in the respective operating chambers and allow the user's hand to be inserted into the corresponding operating glove 300. Therefore, when the corresponding process is carried out, the isolation from the outside can be kept, and the operator can conveniently execute the operation task. The cooperation of the working chamber 100 with the operating glove 300 can be provided and used in the form of a glove box.
In addition, during the processing, the raw materials are processed in a pipelined manner in the working chamber 100, and thus the respective operation sections are constructed to be able to communicate with each other. Thus, the second operating zone 102 can optionally be in communication with or isolated from either or both of the first operating zone 101 and the third operating zone 103 (which can be controlled by valves, not shown). That is, the first operating area 101 can be artificially controlled to communicate with or be isolated from the second operating area 102; accordingly, the second operating region 102 can be artificially controlled to communicate with or be isolated from the third operating region 103.
In order to facilitate the introduction of the raw material and the discharge of the end product (or intermediate product), the first operating area 101 is provided with a first gate that can be closed and opened, and the third operating area 103 has a third opening that can be closed and opened. Based on the structure design, when the phase change material is processed (or pre-processed, pre-processed), the raw material passes through the first operation area 101 (which can be processed or stayed for a suitable designed time) to enter the second operation area 102 (where the raw material is mainly processed), and then enters the third operation area 103, and then can be taken out for subsequent operation.
Since it is desirable that the phase change material is processed under water-free and oxygen-free conditions, the phase change material processing apparatus is provided with the air pump 200. The air pump 200 is selected as an air pump 200 for exhausting various gases, and a vacuum pump, a roots pump, a molecular pump, etc. may be employed. The air pump 200 is connected to the first, second, and third operating areas 101, 102, and 103 and can independently pump air to one or more of the first, second, and third operating areas 101, 102, and 103. In other words, the air pump 200 can perform the air pumping only for any one of the three operation regions at a time. Alternatively, the air pump 200 may only pump any two of the three operating zones at the same time. Alternatively, the air pump 200 may perform air pumping only for any three of the three operation regions at the same time. This can be accomplished by plumbing the air pump 200 to the operating area and installing valves 400 (manual mechanical, or solenoid or other types of valves, 8 valves in fig. 1, with actual number adjustments as needed to add or delete numbers) on each conduit. Further, the opening of each valve 400 (the opening of each valve 400 can be coordinated with the opening time to achieve more complex pumping requirements) can be independently controlled to achieve different pumping requirements for each operating zone for different needs. For example, the degree of evacuation is selected to be different depending on the degree of vacuum.
As mentioned above, the phase change material processing is mainly performed in the second operating area 102, and one of the processing steps involves the crushing of the raw material, and therefore the crushing mechanism 401 is correspondingly disposed in the second operating area 102. The crushing mechanism 401 may be a ball mill or other device known to the applicant or commercially available, and is preferably capable of being installed in the second operating zone 102.
In addition, the processing process also designs that the crushed raw materials are filled in a container for subsequent vacuum hot-pressing sintering. Such a container is provided with a restraint 403 which may be embodied in various molds having a desired cavity. The mould may be made of various high strength materials such as graphite, zirconia, silicon carbide, etc. and the mould cavity may be cubic, rectangular, cylindrical, etc. so that the phase change material blank may be structurally in the form of a sheet, block or rod, wire, etc.
The restraint 403 is disposed within the second operating region 102, and the restraint 403 is provided with a cavity. The powder obtained by crushing the crushing structure can be filled into the cavity of the restraint 403. One non-limiting example of a restraint 403 is a graphite mold. The powder may be sieved prior to filling of the graphite mold to obtain more uniform particles, allowing for more controlled packing density and easy attainment of the desired density. Accordingly, in order to perform screening, a screening device 402, such as a vibrating screen, may be correspondingly disposed in the second operation region 102 of the working chamber 100.
Based on the above processing equipment, the phase change material can be processed in the following manner:
the ball mill and the restrainer 403 are previously installed in the second operating zone 102 of the working chamber 100.
The three operation areas are isolated. The first material opening of the first operation area 101 is opened, the blocky raw material (used for manufacturing the phase change material) to be pulverized is placed in the first operation area 101, and then the first material opening is closed. The first operation area 101 and the second operation area 102 are pumped by the air pump 200, then the first operation area 101 and the second operation area 102 are communicated, the raw material passing through the operation glove 300 is put into the second operation area 102, and then the connection between the first operation area 101 and the second operation area 102 is closed.
After the raw materials are placed in the corresponding equipment by the handling gloves 300 in the first handling area 101 to be crushed and wrapped, the third handling area 103 is pumped by the air pump 200, and then the second handling area 102 is communicated with the third handling area 103, and the wrapped powder raw materials are transferred into the third handling area 103. Then, the second operating area 102 and the third operating area 103 are closed, and the third port of the third operating area 103 is opened, so that the packed powder raw material is taken out.
In other examples, the phase change material processing apparatus may also be provided with a gas supply mechanism 201 (which is located outside the chamber 100) as needed to adjust the processing recipe. As the name implies, the gas supply mechanism 201 is a device for delivering a gas configured in advance to an arbitrarily designated area as desired. In the illustrated example, the gas supply mechanism 201 is coupled to the first operating area 101, the second operating area 102, and the third operating area 103 and is capable of independently injecting gas into any one or more of the first operating area 101, the second operating area 102, and the third operating area 103. As with the gas pump 200 described above, the gas supply mechanism 201 can inject gas into only any one of the three operating zones at a time. Alternatively, the air pump 200 may inject air only into any two of the three operating zones at the same time. Alternatively, the air pump 200 may inject air only into any three of the three operating regions at the same time. Among them, the gas injection object that the gas supply mechanism 201 can provide may be various gases, such as argon, helium, nitrogen, and the like. In an example, the gas can be a mixed gas of hydrogen and nitrogen, wherein the volume ratio of the hydrogen can be 0-5.0%, such as 1%, 1.6%, 2.2%, 3.5%, 4.8%. The higher the proportion of hydrogen, the better the reducing property (ability to prevent oxidation) thereof, but at the same time, the proportion of hydrogen is controlled so as to prevent flammability of the mixed gas. Typically the maximum hydrogen content is less than 5.0% by volume.
Further, the phase change material processing equipment may also be provided with a packaging mechanism 404 according to functional requirements. As previously discussed, the comminuted material is loaded into a restraint 403 (e.g., a graphite mold), and to avoid the adverse effects of water and oxygen on the powdered material in the graphite mold, the enclosure mechanism 404 is configured to hermetically enclose the restraint 403 in an oxygen and water free environment. In an alternative example, the packaging mechanism 404 is selected to be a plastic packaging machine that can complete plastic packaging in a mold.
Further, as before, the phase change material processing equipment may also be provided with other functional equipment. For example, one or more of the first operating zone 101, the second operating zone 102, and the third operating zone 103 are provided with environmental condition detectors including one or more of a temperature sensor, a humidity sensor, and an oxygen sensor.
In one general option, the ambient condition detector is selected to be a humidity sensor and an oxygen sensor, corresponding to the moisture and oxygen concentration. The environmental condition detector may be installed in the second operating region 102. It is understood that the detected data of each sensor can be displayed graphically and digitally through the display to facilitate the user to know the conditions of the device (such as humidity and oxygen concentration in the working chamber). In addition, the processing equipment may be equipped with alarms for warning when the humidity or oxygen content exceeds a desired value. For example, each sensor is connected to a controller. The controller can receive the data of the sensor and compare the data with a threshold value preset by an operator. And alarming when the environmental detection value exceeds a threshold value (an audible and visual alarm, a vibration alarm and the like). The controller may be any type of electronic component or collection of components capable of certain data storage and processing. Such as a Central Processing Unit (CPU), a Micro Control Unit (MCU), an editable logic controller (PLC), a Programmable Automation Controller (PAC), an industrial control computer (IPC), a Field-Programmable Gate Array (FPGA), and so on.
The processing equipment of the phase change material can be further provided with a shell based on the requirement of integrated design. The working chamber 100, the air pump 200, the crushing mechanism 401, and the restrainer 403 are provided in the housing. In the example having the gas supply mechanism 201, the packing mechanism 404, and the environmental condition detector, the working chamber 100, the air pump 200, the crushing mechanism 401, the restrainer 403, the gas supply mechanism 201, the packing mechanism 404, and the environmental condition detector are also provided within the housing. When the phase change material processing apparatus is provided with a cabinet, the processing equipment can be mounted and transferred as a whole.
Based on the foregoing processing apparatus, a method of processing a phase change material is provided in an example.
The processing method comprises the following steps:
an enclosed space is provided, and oxygen and water are excluded from the enclosed space.
The enclosed space is located within the working chamber 100 and can be implemented and realized by isolating any one operating zone from the adjacent operating zones and then pumping by the air pump 200. The enclosed space may be a first operating area 101, a second operating area 102 and a third operating area 103. And generally at least in such an arrangement, the second operating region 102 is always in a protective gas environment at steady state operation.
The enclosure is depleted of oxygen and water may be achieved by evacuating a designated area of the chamber 100 to a vacuum. Alternatively, a designated region of the chamber 100 is first evacuated to a vacuum, and then an auxiliary gas is injected thereinto as needed. The auxiliary gas ensures that the raw materials are not adversely reacted when they are processed. That is, the closed space is in a vacuum state or filled with an inert gas or a reducing gas. In some examples, the enclosed space is at a positive pressure relative to atmospheric pressure when the enclosed space is filled with an inert gas or a reducing gas. The positive pressure here may be a proper positive pressure, such as a slight positive pressure, to avoid the difficulty of realization due to an excessive pressure, or the strength of the apparatus needs to be adjusted. That is, the pressure of the auxiliary gas in the closed space is higher than the standard atmospheric pressure. For example, where the local standard atmospheric pressure is 101.325kPa (1.01325. multidot.105 Pa), then the micro-positive pressure may be 1.064. multidot.105～1.115·105Pa。
Wherein the inert gas may be argon. The reducing gas may be a mixed gas of nitrogen and hydrogen. The volume content of hydrogen in the mixed gas is 2-5%. Alternatively, the volume content of hydrogen in the mixed gas is 4%.
The raw material is pulverized into powder in the closed space, and the raw material is derived from a compound formed by elements constituting the phase change material.
Through on-off adjustment of each operation area, the cooperation of the air pump 200 and the gas supply mechanism 201, the raw material is delivered to the corresponding operation area from which water and oxygen are removed, and then the raw material is pulverized by the pulverization mechanism 401. As an example, the raw material for making the phase change material may be a compound formed of elements constituting the phase change material obtained by vacuum melting. For example, the compound may be selected to be a chalcogen compound. The chalcogen compound may include, but is not limited to, Ge2Sb2Te5、Cx[Ge2Sb2Te5]y、Sc0.2Sb2Te3、Ta0.3Sb2Te3、InGe2Sb2Te5、CuGe2Sb2Te5GeSbTeIn and AgInSbTe, wherein the value of x ranges from 1 to 18 at%, and x + y is 100 at%. at% represents the atomic content (percentage) of the element. And at Cx [ Ge ]2Sb2Te5]In the y compound, C represents carbon, so that the compound refers to Ge doped with carbon in x atomic ratio2Sb2Te5. In other examples, titanium (Ti) vs Ge may also be used2Sb2Te5And (6) doping.
And constraining the powder in a preset cavity in a closed space and carrying out vacuum hot pressing treatment.
After the material is comminuted, it is then placed in a closed chamber and constrained to a particular shape for vacuum autoclave processing. The powder is packed in the constraints 403 and the way of its state can be adjusted appropriately to meet the actual needs or requirements for the properties of the final product. The adjustment of the loading state can be achieved by selecting the loading density and the particle size of the powder. For example, before confining the powder in the closed space to the preset cavity, the processing method comprises the following steps: the powder was sieved. Alternatively, the density of the powder filled in the restraint 403 is defined to be 66% or less. Wherein the density is (actual density/theoretical density) × 100%.
In order to make the application easier for the person skilled in the art to carry out, two solutions for handling raw materials for phase change materials in a processing plant are presented by way of example.
The first scheme is as follows: the ball mill and the massive phase-change material to be milled are placed in a completely closed working chamber 100, and the working chamber 100 is vacuumized to be less than 10 < -3 > Pa. The reducing gas H2: N2 (ratio 4% H2) is then introduced into the chamber 100, maintaining a slight positive pressure relative to the ambient atmospheric pressure. In this atmosphere, after the ball mill completes pulverizing, sieving of the powder size is performed. The sieved powder was placed in a graphite mold. The graphite mold with the charge is sealed with a self-locking plastic bag. The interior of the plastic bag should contain an oxidation-resistant reducing gas;
the second scheme is as follows: the ball mill, the screening device, the graphite mold and the massive phase-change material to be pulverized are placed in a completely closed working chamber 100, and then are pumped to less than 10 DEG-3Pa of vacuum. Ar gas is then introduced into the glove box to create a slight positive pressure against the periphery. In this atmosphere, after the ball mill completes pulverizing, sieving of the powder size is performed. The sieved powder was placed in a graphite mold. The graphite mold with the charge is sealed with a self-locking plastic bag. The interior of the plastic bag should contain protective argon against oxidation and moisture.
After the above two schemes are processed, the raw materials for making the phase-change material are crushed in an environment without water and oxygen, filled in a container with a determined form and packaged to isolate air and water vapor. In this manner, the hot pressing process can be performed in a hot pressing apparatus, as described below.
Taking the mould filled with the powder material out of the plastic bag in an environment with controlled humidity and temperature, then loading the mould into a cavity of a vacuum hot press within 30 minutes, closing a furnace cover, and starting the processes of vacuumizing and hot pressing.
If it is desired to wait for a vacuum hot press, the mold must be kept in a desiccator filled with a protective gas (H2[ 4% ]: N2 or argon) to prevent oxidation or adsorption of moisture from the environment.
In practice, the content of [ O ] of the post-prepared phase change material treated by the applicant with the above safeguard can be controlled to <400 ppm.
Accordingly, the operation flow of the processing equipment is as follows:
(1) all the equipment including the ball mill (crushing mechanism 401), the powder screening machine (screening equipment 402), the die (restraint 403), and the necessary packaging facilities (packaging mechanism 404) are placed in the working area (second operation area 102) of the closed glove box through transition boxes at both ends under atmospheric pressure;
(2) the vacuum VAT valve 400 of the feed port (third port) of the third operating zone 103 of the glove box was closed. Connecting the working area (the second operation area 102) and the discharging transition cabin (the third operation area 103) with a vacuum pump (an air pump 200), and vacuumizing the two cavities to ensure that the vacuum degree reaches 10 < -2 > to 10 < -3 > Pa;
(3) the working zone (second operating zone 102) and the discharge transition chamber (third operating zone 103) are filled with argon, which is an inert gas, or a reducing gas, H2 (0-5.5%) -N2, so that the pressure of the two chambers is slightly positive with respect to the atmospheric pressure. The specific pressure range is 1.05-1.1 atm, and the corresponding pressure is 1.064 & 105-1.115 & 105 Pa. In this state, the system is in a charging operating state.
The block material to be made into powder is loaded into a loading transition chamber (a first operation area 101) which is placed under the atmospheric pressure state, and the loading transition chamber is vacuumized to ensure that the vacuum degree reaches 10 < -2 > to 10 < -3 > Pa. Then, inert gas argon or reducing gas H2 (0-5.5%) -N2 is fed into the charging cabin (the first operation area 101), so that the pressures of the charging cabin (the first operation area 101) and the working cabin (the second operation area 102) are balanced and are in a pressure range of 1.05-1.10 atm. At this time, the whole system is in a state of preparing powder.
Opening a vacuum VAT valve 400 at the end of the charging cabin, and putting the blocky materials into a ball mill in a protective gas state for milling; after powder preparation is finished, putting the powder into a powder sieving machine, and sieving the powder according to the size; loading the screened powder into a graphite die to form a blank; and packaging the mold filled with the powder by using a plastic bag, and placing the whole mold filled with the powder in a plastic package of protective gas.
The vacuum VAT valve 400 of the discharge chamber (third operating area 103) is opened, the packed graphite molds are transferred to the discharge chamber, and the vacuum VAT valve 400 of the discharge chamber is subsequently closed. And opening a door (a third material port) of the discharging cabin, and taking out the packaged graphite mold.
The raw material after the above treatment steps can be subjected to subsequent hot-pressing sintering operation. In an environment with the controlled temperature of 15-20 ℃ and the relative humidity of 25% -30%, the packaged graphite mold is processed in two ways:
(1) if the vacuum hot-pressing furnace is ready, the graphite mold is placed into the cavity of the vacuum hot-pressing furnace within 30 minutes, the furnace cover is closed, and the process of vacuumizing and hot-pressing is started.
(2) If the vacuum autoclave is not ready, the packaged graphite mold must be stored in a protective dry box (descator) with a protective gas such as N2 or Ar. The temperature in the drying oven is controlled between 40 ℃ and 50 ℃, the relative humidity is less than 1 percent, and the next prepared vacuum autoclave is waited.
The above procedure completes a complete process from powder production to vacuum hot press charging in a protective gas and controlled temperature range. The next process repeats the above steps.
It is worth noting in particular that: the working area (the second operation area 102) of the system can be always in the protective inert gas or reducing gas H2 (0-5.5%) -N2 atmosphere (except for the system needing maintenance), so that a large amount of inert gas or reducing gas can be saved. The inert gas or reducing gas of the charging chamber and the discharging chamber is required to be replaced when the system works. The glove box system is internally provided with a detection instrument for detecting temperature, humidity and O content. The whole system should be placed in an environment with temperature controlled at 15-20 deg.C and relative humidity controlled at < 30%.
In general, the example processing equipment employs a feed and discharge chamber design, with the working zone protective atmosphere always being an inert or reducing atmosphere, which greatly improves the ability of the material to avoid oxidation or doping with other impurities. By this design, a large amount of inert or reducing gas H2 (4%) -N2 can also be saved. When the phase change material is used for processing the manufacturing raw materials of the phase change material, the generation of oxidation and adsorption of oxygen or water vapor can be prevented, and the measured content [ O ] of the phase change material can be lower than 400 ppm.
In addition, in the protective atmosphere of the working area, the embryo in the mold is pressed to have the initial density of about 60 percent, so that the embryo can be further prevented from adsorbing oxygen or water vapor outside the closed glove box. Also, the higher the initial density in the working area, the greater its ability to resist oxygen or water vapor adsorption.
In the working area of the closed glove box, after the graphite mold is filled with powder materials, the graphite mold is wrapped by a self-locking plastic bag. This step can prevent the adsorption of oxygen or water vapor outside the working area. Sometimes, in order to further prevent the moisture or oxygen from being absorbed outside the working area, the powder can be wrapped by double plastic bags, so that the oxygen or the moisture can be more effectively prevented from being diffused into the powder.
In normal production flow, sometimes the vacuum hot press and the powder making process are not completely seamless. In another example, the processing facility may incorporate a dry box with a controlled atmosphere as a transition to wait for the next process press to be ready. The controlled atmosphere is free of [ O ] or reducing atmosphere, and needs a certain temperature to avoid moisture in the environment. The process can play a very important role in controlling the content [ O ] of the phase-change material in the whole process.
The following describes the processing method and apparatus of the phase change material in detail with reference to the embodiments.
The first embodiment is as follows: low [ O ] content Ge2Sb2Te5And (3) forming a compound.
The total weight is 5.5 kg, and the purity is>Vacuum melting 4N of block chalcogenide phase change materialMaterial compound Ge2Sb2Te5And putting the mixture into a feeding cabin of a closed glove box. Pumping the feeding cabin to 5.6.10-3 Pa by a vacuum pump, then opening to fill reducing gas H2 (4%) -N2 into the cavity until the pressure reaches 1.06atm (-1.074.10)5Pa) is added. At the moment, the pressure of the reducing gas H2 (4%) -N2 in the working area and the discharging cabin is about 1.05atm, the temperature is 18 ℃, and the relative humidity is<1 percent. The vacuum VAT valve 400 at the end of the charging chamber is opened to introduce Ge2Sb2T5The bulk material is placed in a ball mill pulverizer. The vacuum VAT valve 400 at the loading bay end is closed. The process flow of ball milling powder preparation is started. After completion of milling, the powder is transferred to a sieving device. After sieving, the powder was loaded into a graphite mold with an inner diameter of 460mm ID and a little pressure was applied to achieve-63% densification of the embryo in the mold. The graphite mold containing the powder was wrapped in a self-locking plastic bag, the interior of which should be filled with reducing gas H2 (4%) -N2. The vacuum VAT valve 400 at the discharge end is opened, the plastic bag with the powder mold is placed stably in the discharge chamber, and then the vacuum VAT valve 400 at the discharge end is closed. Opening the discharging port, taking out the plastic bag with the mold, immediately closing the discharging port, and vacuumizing the cavity to 5.6-10-3After Pa, immediately filling reducing gas H2 (4%) -N2 to keep the pressure of the discharging cabin at 1.05-1.15 atm, the temperature at room temperature and the relative humidity<1 percent, preparing the next pulverizing and charging process. And (4) after the graphite mold packaged by the plastic bag is taken out, the graphite mold is placed into a cavity of a vacuum hot-pressing furnace within 18 minutes, and the vacuum is pumped to prepare the hot-pressing process flow. The oxygen content of the phase-change material target material finished through the procedures is 180ppm according to the measurement of an LECO instrument of the EAG.
Example two: phase change material C containing [ O ] in an amount of less than 300ppm5(Ge2Sb2Te5)95Formation of at% chalcogenides.
The total weight is 5.8 kg, and the purity is>Vacuum melting 4N, and making it into block sulfur family phase change material compound C5(Ge2Sb2Te5)95Putting the mixture into a feeding cabin of a closed glove box at percent. Will be provided withPumping the feeding cabin to 5.4.10-3 Pa by a vacuum pump, and then opening to fill inert gas argon into the cavity until the pressure of the inert gas argon reaches 1.08 atm. At the moment, the argon pressure of the working area and the discharge cabin is about 1.07atm, the temperature is 17 ℃, and the relative humidity is<1 percent. Opening the load chamber end vacuum VAT valve 400, and5(Ge2Sb2Te5)95the at% bulk material was placed in a ball mill pulverizer. The vacuum VAT valve 400 at the loading bay end is closed. The process flow of ball milling powder preparation is started. After completion of milling, the powder is transferred to a sieving device. After sieving, the powder was loaded into a graphite mold with an inner diameter of 460mm and a little pressure was applied to achieve-60% compaction of the embryos in the mold. The graphite mould filled with the powder is wrapped by a self-locking plastic bag, and the interior of the plastic bag is filled with argon. The vacuum VAT valve 400 at the discharge end is opened, the plastic bag with the powder mold is placed stably in the discharge chamber, and then the vacuum VAT valve 400 at the discharge end is closed. Opening the discharging cabin door, taking out the plastic bag with the mold, immediately closing the discharging cabin door, vacuumizing the cavity to 5.7.10-3 Pa, and immediately filling argon to keep the pressure of the discharging cabin at 1.06atm, the temperature at room temperature and the relative humidity<1 percent, preparing the next pulverizing and charging process. And (3) after the graphite mold packaged by the plastic bag is taken out, the graphite mold is placed into a cavity of a vacuum hot-pressing furnace within 20 minutes, and the vacuum is pumped to prepare the hot-pressing process flow. The oxygen content of the phase change material target material completed through the above procedures, measured according to LECO of EAG, is 250 ppm.
Example III phase-change chalcogenide InGe with low [ O ] content2Sb2Te5And (4) preparing the target material.
The total weight is 5.9 kg, and the purity is>4N, using vacuum melting massive sulfur group phase change material compound InGe2Sb2Te5And putting the mixture into a feeding cabin of a closed glove box. Pumping the feeding cabin into 5.9-10 deg.c with vacuum pump-3Pa, then starting to fill the inert gas argon into the cavity until the pressure reaches 1.05 atm. At the moment, the argon pressure of the working area and the discharge cabin is about 1.06atm, the temperature is 18 ℃ at room temperature, and the relative humidity is high<1 percent. The vacuum VAT valve 400 at the end of the charging chamber is opened to introduce InGe2Sb2Te5The bulk material is placed in a ball mill pulverizer. The vacuum VAT valve 400 at the loading bay end is closed. The process flow of ball milling powder preparation is started. After completion of milling, the powder is transferred to a sieving device. After sieving, the powder was loaded into a graphite mold with an inner diameter of 460mm and a little pressure was applied to achieve-66% compactness of the embryo in the mold. The graphite mould filled with the powder is wrapped by a self-locking plastic bag, and the interior of the plastic bag is filled with argon. The vacuum VAT valve 400 at the discharge end is opened, the plastic bag with the powder mold is placed stably in the discharge chamber, and then the vacuum VAT valve 400 at the discharge end is closed. Opening the discharging port, taking out the plastic bag with the mold, immediately closing the discharging port, and vacuumizing the cavity to 5.8-10-3After Pa, argon is immediately filled in to keep the pressure of the discharging cabin at 1.06atm, the temperature is room temperature, and the relative humidity is<1 percent, preparing the next pulverizing and charging process. After the graphite mold packed in the plastic bag is taken out, the graphite mold is put into a drying oven with controlled atmosphere within 5 minutes. The temperature in the drying oven was 50 ℃ and the relative humidity<1% and filled with protective inert gas N2. After 5 hours, the vacuum hot-pressing furnace is ready, the graphite mold filled with the powder is placed into the cavity of the vacuum hot-pressing furnace within 24 minutes, the furnace cover is covered and vacuumized, and the hot-pressing process flow is prepared. The oxygen content of the phase change material target material finished through the procedures is 320ppm measured according to LECO of the EAG.
While particular embodiments of the present application have been illustrated and described, it would be appreciated that many other changes and modifications can be made without departing from the spirit and scope of the application. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this application.
Claims (7)
1. A method for processing a phase change material, the method being implemented by processing equipment, the phase change material being suitable for manufacturing a non-volatile memory chip, the processing equipment comprising:
the working chamber is provided with a first operation area, a second operation area and a third operation area which are sequentially arranged and are respectively provided with operation gloves, the second operation area can be optionally communicated or isolated with any one or two of the first operation area and the third operation area, the first operation area is provided with a first material opening capable of being closed and opened, and the third operation area is provided with a third opening capable of being closed and opened;
the air pump is connected with the first operation area, the second operation area and the third operation area and can respectively and independently pump air to any one or more of the first operation area, the second operation area and the third operation area;
a shredding mechanism located within the second operating zone;
the restraint device is positioned in the second operation area and is provided with a cavity;
the gas supply mechanism is connected with the first operation area, the second operation area and the third operation area and can respectively and independently inject gas into any one or more of the first operation area, the second operation area and the third operation area;
an enclosure mechanism configured to close-pack the restraint such that the restraint is enclosed in an oxygen and water free environment;
the processing method comprises the following steps:
providing a closed space by the working chamber and the air pump, wherein the closed space is excluded from oxygen and water;
injecting reducing gas into the closed space by using the gas supply mechanism to form positive pressure, wherein the reducing gas comprises mixed gas of nitrogen and hydrogen, and the volume content of the hydrogen in the mixed gas is 2-5%;
pulverizing a raw material, which is a compound formed from elements constituting the phase change material, into powder in the closed space by the pulverization mechanism;
constraining the powder in a preset cavity in the closed space, wherein the density of the powder filled in the constraining device is less than or equal to 66%, and sealing the preset cavity through the packaging mechanism;
and taking out the sealed preset cavity in which the powder is constrained from the working chamber, and carrying out vacuum hot-pressing treatment.
2. The method of processing a phase change material as claimed in claim 1, wherein one or more of the first, second and third operating zones are provided with an ambient condition detector comprising one or more of a temperature sensor, a humidity sensor and an oxygen sensor.
3. The method of processing a phase change material as claimed in claim 1, wherein the phase change material processing apparatus includes a housing, and the working chamber, the air pump, the pulverization mechanism, and the restrainer are provided in the housing.
4. The method according to claim 1, wherein the volume content of hydrogen in the mixed gas is 4%.
5. The method according to claim 1, wherein the compound formed from the elements constituting the phase change material is obtained by vacuum melting, and the compound comprises a chalcogen compound.
6. The method according to claim 5, characterized in that said chalcogen compound comprises Ge2Sb2Te5、Cx[Ge2Sb2Te5]y、Sc0.2Sb2Te3、Ta0.3Sb2Te3、InGe2Sb2Te5、CuGe2Sb2Te5GeSbTeIn and AgInSbTe, wherein the value range of x is 1-18 at%, and x + y is 100 at%.
7. The method for processing a phase change material according to any one of claims 1 to 5, wherein before constraining the powder in the closed space to a predetermined cavity, the method comprises: the powder is sieved.
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